Reactor manufacturing method for a fuel cell processor
A method to produce a catalytic bed is initiated by forming apertures in a predetermined pattern on a strip or segment of thin foil. A pattern of desired channels is formed into the apertured foil, for example, as a herringbone pattern. The patterned foil is heat treated, and the surfaces of the foil are provided with at least one washcoat and at least one catalyzed coat, and cured. Cured foil in strip form is rolled into a multi-layer coil, or cured foil in segment form is stacked in multiple segment layers, to produce a desired geometric shape of the catalytic bed. The channels between layers of foil are offset in each successive layer to preclude channel nesting. The offset channels and apertures provide turbulent longitudinal and radial flow of a desired material throughout the catalytic bed.
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The present invention relates to a catalytic reactor for a fuel cell system, and more specifically to a method for manufacturing a catalytic reactor having a perforated metal support providing uniform wash coat catalyst loading and distribution, and turbulent flow throughout the reactor.
BACKGROUND OF THE INVENTIONOperating conditions of a catalyst system in an exemplary industrial process catalytic reactor cover a relatively small range of variables. The flow ranges in an exemplary industrial process are no more than 4 or 5:1, the inlet flow and mixing conditions are well defined, and the reaction zones are also closely controlled to produce temperature profiles that are maintained within a narrow range. Start conditions are carefully controlled to assure the catalyst and reactor are performing according to prescribed conditions. This type of operation leads to catalyst system designs that have less demanding requirements compared to operations of similar processes where temperature and performance controls must be held tightly over a wide range of dynamic operating conditions.
One of the most familiar deviations from the exemplary industrial process reactor is the automotive exhaust emission control catalyst system. In this system, the start and operating conditions are significantly different. Temperature difference and reactant ratio from start to operating conditions can vary rapidly. This catalyst system also operates with wide ranges of throughput, which can vary as much as 50:1, with space velocities in excess of 100,000 hr−1, and high heat release (significantly higher than the exhaust emission converter) over the operating range. Because of their application, catalytic reactors must be compact as well. This demands the development of creatively designed catalyst systems that can be prepared by methods commercially conceivable.
One commercially available approach for exhaust emission control catalysts employs honeycomb monoliths for the reactor. In the operation of honeycomb monolith catalytic reactors on vehicles, thermal profile and conversion are maintained over the wide engine operating conditions, without raising system back pressure, by combining the catalyst bed structure variables, associated with the honeycomb monolith, with catalyst preparation procedures. By increasing the honeycomb cell or channel density, i.e., decreasing the cell size and reducing the wall thickness, the fluid dynamics of the reactant gases and reactions taking place over the entire operating range are improved over larger cell sizes, thus helping to maintain reasonably well-controlled temperature profiles and subsequently providing better durability.
Through the use of honeycomb monolith catalyst systems, catalyst type and loading over the length of the catalyst/converter flow path can offer reaction and temperature profile control, while simultaneously meeting the conversion required via catalyst loading and control of material availability during catalyst preparation. Improved catalyst materials, preparation procedures, and structure were developed concurrently with refinement of the catalyst structure in achieving this higher performance.
Drawbacks exist, however, for honeycomb monolith catalyst systems in fuel cell fuel processor system applications. The heat flux (heat release rate and quantity) and the relative ratio of size to degree of reaction complexity associated with an automobile exhaust catalytic reactor are relatively small compared to the primary reactor of a fuel cell fuel processor. Also, automobile honeycomb monolith exhaust catalytic reactors often detrimentally develop laminar flow through large sections of the straight, continuous, channels of their honeycomb structure. This creates mass transport problems, and the only effective means for distributing heat is axially, along the length of the channels. If any over-temperature condition develops in the inlet section, where turbulence does exist, or if any blockage or unequal distribution of inlet feed exists, there is no means by which the reactants can migrate from one channel to another in a single monolith, or redistribute the reactant flow some distance downstream from a blockage.
Modification of the honeycomb monolith assembly provides some improvement. By providing many “slices” of a honeycomb monolith, wherein the channel alignment of each slice is offset, conditions closer to continuous mixing and redistribution phenomena take place. This approach also has drawbacks, however, in that washcoating and catalyst loading are performed after assembly, which can result in non-uniform washcoating and catalyst loading throughout the offset monolith. After-assembly washcoat and catalyst loading is both extremely difficult and cost ineffective to both prepare and subsequently to retain the catalyst structure without physical damage to the washcoat or catalyst layer(s).
Another catalyst structure that has been considered for automotive and fuel processor applications is the foam support. This structure potentially provides the desired tortuous flow path that can assist in maintaining turbulent mixing of the reactants through the catalyst bed, thereby enhancing mass and heat transport properties. The disadvantage of this support structure is similar to the “sliced honeycomb monolith” in that washcoating and catalyzing the surfaces requires forcing a slurry of the washcoat and/or catalyst material through its webbed structure after assembly. Washcoating these supports uniformly throughout the structure can be very problematic, particularly when cell density is relatively high. In addition, these supports have been found to be very non-uniform in both cell size and cell distribution. This results in areas where blockages occur because of fabrication faults, making coating and distribution activity less controlled. A further disadvantage is that backpressure through these monoliths is higher than for the honeycomb monoliths.
Based on the above, there is a need for tailored catalyst systems that meet the desired activity of a fuel cell fuel processor (reactor) over a wide range of operating conditions. Catalyst system requirements for an onboard hydrocarbon (i.e., gasoline, LPG or NG) conversion processor have both similarities and significant differences from the previously mentioned examples. Similarities include: 1) the choice of catalyst and catalyst loading must be commensurate with the reaction processes and cost requirements; and 2) heat transfer and control of temperature are critical to maintaining life and conversion selectivity.
An optimal catalyst system design for fuel processor operation should provide a variety of flow paths throughout the length of the catalytic reactor, in order to induce turbulent flow to accommodate the reaction flux over the entire set of operating conditions, without compromising (1) the catalyst loading or type, (2) life of either the catalyst or reactor, (3) pressure drop, or (4) performance, i.e., conversion/selectivity. Uniformly controllable washcoat and catalyst loading is not available with the honeycomb or foam support design catalytic beds. A catalyst manufacturing method is therefore required which also incorporates controlled, but passively variable flow paths throughout the catalyst bed to promote turbulent flow throughout, the ability to control washcoat and catalyst loading prior to assembly of the bed, and an assembly which permits either the washcoat or the catalyst or both washcoat and catalyst to be varied through the catalytic bed.
SUMMARY OF THE INVENTIONTo overcome the drawbacks and disadvantages of the above design approaches, and to meet the necessary design conditions noted, disclosed herein is a method of forming a catalyst bed. The method provides a metal support comprising a metal foil perforated with a plurality of apertures or holes of different sizes and shapes integrated throughout the foil. The perforated foil is then heat treated, washcoated, catalyzed and cured. The bed is assembled by either layering individual segments of the perforated, washcoated and catalyzed foil or spirally rolling a predetermined length of prepared foil strip. By combining shaped sections, in either segments or a rolled coil, with a plurality of apertures, a uniform longitudinal and radial flow path is provided throughout the bed, thus providing for controlled temperature and reaction rate throughout the bed.
The invention method provides catalyst beds possessing the necessary properties to permit successful operation of a fuel cell fuel processor over a wide range of variable conditions. Several embodiments of the invention are disclosed, each incorporating at least one of two aspects associated with catalyst fabrication. In one aspect of the invention, the catalyst system is based on forming metal foil which is replete, to the extent and need required, with apertures (holes) of size and pattern concomitant with the catalyst system design operating requirements. The perforated metal foil is then shaped into any of various configurations, such as chevrons, herringbones, waves, “Quonset huts”, dimples, etc. The above features, as well as the frequency, pitch, depth, and pattern of the foil configuration are controlled to provide either multiple segments or windings of a roll, neither of which permit direct overlapping of these features that would allow “nesting”, or collapsing of one segment or rolled layer onto another. Uniform flow paths throughout the catalytic bed are therefore provided in this aspect of the invention.
In another aspect of the invention, the washcoat and catalyst are applied onto the segments or strips of the metal foil catalyst support. Based on the use of segments which are later stacked, or strips which are later coiled, the washcoat and catalyst application procedure can advantageously utilize various known methods of applying the washcoat and catalyst prior to assembly of the catalytic bed. Known methods such as spraying, dipping, or growing the washcoat on the surface of the metal can then be used. The catalyst is applied as is known in the art as an individual coat after the washcoat, or is combined and applied together with the washcoat.
Application of the washcoat and catalyst at this stage eliminates the need to use the “slurry” system of washcoating and catalyzing the catalyst bed after assembly of the bed, which is required by the honeycomb and foam support designs. A different washcoat or catalyst can be applied to different layers of foil, or on different areas of a single layer, or the catalyst volume can be varied throughout. Following the washcoat and catalyst application, the coated metal is cured, preferably before but also optionally after assembly into the catalytic bed. The ability to grade the catalyst throughout the bed, provide different catalysts in different segments of the bed, or modify the washcoat type and thickness throughout the bed is therefore provided in this aspect of the invention.
In one preferred embodiment of the invention, a method to manufacture a catalytic bed is provided, comprising the steps of: providing a metal foil; disposing a desired aperture pattern in the metal foil; processing the metal foil having the desired aperture pattern into a desired foil pattern; heat-treating the desired foil pattern for a washcoat; coating the heat-treated foil pattern with the washcoat and a catalyst; and forming a geometric configuration of the catalytic bed from the coated foil pattern.
In another preferred embodiment of the invention, a method is provided to manufacture a catalytic bed for an automobile fuel processor comprising the steps of: providing a metal foil; disposing a desired aperture pattern in the metal foil having a plurality of both aperture shapes and sizes; processing the metal foil having the desired aperture pattern into a desired foil pattern; heat-treating the desired foil pattern for a washcoat; coating the heat-treated foil pattern with at least one washcoat and at least one catalyst; applying the catalyst over preselected areas of the coated foil pattern in a graded formation; forming a geometric configuration of the catalytic bed having at least two layers of the coated foil pattern; and positioning each layer of the catalytic bed to provide a non-overlapping aperture configuration.
In yet another preferred embodiment of the invention, a method is provided to provide turbulent flow in all regions of a catalytic bed comprising the steps of: providing a metal foil; disposing a desired aperture pattern in the metal foil; processing the metal foil having the desired aperture pattern into a desired foil pattern; heat treating the desired foil pattern; coating the heat-treated foil pattern with at least one washcoat and at least one catalyst; forming a geometric configuration having successive layers of the coated foil pattern; locating each of the successive layers to offset the aperture pattern between any layer and a next successive layer; and combining the successive layers to provide a network of flowpaths providing for a turbulent flow of a desired material throughout the catalytic bed in both an axial direction and a radial direction.
In still another preferred embodiment of the present invention, a catalytic bed for a fuel processor is provided, comprising: a metal foil; a preselected set of apertures being formed in said foil; said apertured foil being configured into a desired foil pattern; said foil pattern having at least one heat treated surface; each heat treated surface having at least one washcoat and at least one catalyst coat; a plurality of said washcoated and catalyst coated foil surfaces being formed into a geometric pattern having a plurality of adjacent layers; and the foil pattern of each layer has a foil pattern mismatch to each adjacent layer foil pattern to preclude foil pattern nesting between adjacent layers.
Because the invention provides for strips or sheets that can be assembled in a variety of configurations, such as layers of sheet segments or rolls of foil, the catalyst and washcoat applications can incorporate various compositions and formulations that can be installed into the assembly of a catalyst bed. Assembly of the catalyst bed can utilize any of numerous choices including: (1) layering of sheet segments that are each differently catalyzed; (2) layering of sheet segments that are graded with different catalyst/washcoat over two dimensions of the foil; or (3) rolling separate strips which are selectively adjoining each other over the centerline length of the bed, with differing aperture designs and catalyst/washcoats to provide a desired flow and activity profile for control of a reaction.
Combining the perforated metal having desired designs for flow distribution with subsequent catalyst preparation provides for catalyst bed flow patterns that can be modulated over the catalyst bed dimensions, either from wall to wall and over the length (in the case of a square or rectangular shaped reactor), or from wall to centerline and over the length (in the case of a tubular or conical shaped reactor). Also, by selectively combining specific catalyst type and activity, controlled by preparation and catalyst material choices, in combination with the metal foil configuration, controlled by the aperture and aperture shape choices, desired mass and heat transport properties are then matched, associated with the particular reactions to be controlled in a given process reactor.
A catalyst bed prepared by the method of the invention exhibits additional properties throughout the reactor. These additional properties include: selectivity of the catalyst for reaction rate control and subsequent control of temperature, selectivity of the catalyst to control production of intermediate chemical species which inhibit carbon formation, and distribution of reacting species in the gas phase to create a more uniform temperature profile under all conditions.
Further areas of applicability of the present invention will become apparent from the detailed description provided hereinafter. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
The present invention will become more fully understood from the detailed description and the accompanying drawings, wherein:
The following description of the preferred embodiment(s) is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. Variations that do not depart from the jist of the invention are intended to be within the scope of the invention. Such variations are not to be regarded as a departure from the spirit and scope of the invention.
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The preferred method of assembly lends itself to fabricating a graded or multi-catalyst bed. In this regard, different amounts of catalyst may be applied on a single sheet in step (6) or different catalyst materials may be applied on different individual metal foil sheets which are formed into the desired geometric pattern in step (8).
Referring back to
The present invention has the benefit over the conventional honeycombed design of providing 3-dimensional flow capability. For example, in the cylindrical embodiment shown in
The present invention utilizes conventional washcoats known in the art and may comprise an alumina material washcoated to a desired thickness on the metal support structure. Normally the catalyst is added after the washcoat, however, with this invention the catalyst may be added together with the washcoat and applied in one or more layers on each metal foil layer. Exemplary catalyst loading is a very low percentage of the washcoat loading. Particle size of the catalyst is in the nanometer range.
The method described herein is not limited to specific uses of catalytic reactors. Various catalytic uses may be applicable. Exemplary uses include, but are not limited to reactors for partial oxidation, steam reforming, and water/gas shift. Further uses include catalytic converters, ammonia synthesis requiring controlled gradients within the bed, preferential oxidation reactors and combustors.
Since each foil sheet or segment is individually formed, washcoated and catalyzed, this method also permits the use of different catalyst materials and/or loadings throughout the reactor and the potential to provide gradation of one or more catalysts throughout the reactor which provides the added benefit of minimizing costly catalyst material used.
Disclosed is a method for assembling catalyst beds that incorporates the use of multiple design configurations of the catalyst support and the methods for applying catalysts as a result of this assembly process. Application of this process of using any of several different catalyst support configurations provides a more flexible and versatile method for producing fuel cell fuel processor catalytic reactors. These catalyst beds may exhibit higher activity in smaller volumes because of improved heat and mass transfer, reduced precious metal loading, improved cost, improved passive control, and increased turndown capability in comparison to conventional packed beds, foam support or honeycomb monolith beds. Flexibility in reactor design is also provided, as a result of the variability possible to tailor changes in the flowfield, catalyst loading and catalyst type throughout the reactor volume to match reaction conditions and demands.
Claims
1. A method to manufacture a catalytic bed for an vehicle fuel processor comprising the steps of:
- providing a metal foil having a desired aperture pattern and a plurality of both aperture shapes and sizes;
- shaping the metal foil to form a repeating pattern;
- heat-treating the patterned foil in preparation for at least one washcoat;
- coating the heat-treated foil pattern with at least one washcoat;
- applying at least one catalyst over a preselected area of the coated foil pattern to form a graded catalyst formation;
- forming a geometric shape from at least two layers of the coated foil pattern to form the catalytic bed; and
- positioning a first layer of the catalytic bed and a second layer of the catalytic bed at a corresponding position to preclude overlapping the aperture pattern.
2. The method of claim 1 comprising the further steps of:
- rolling the coated foil pattern around a mandrel; welding an end of the rolled coil to the mandrel; and coiling the rolled coil about the mandrel to form the geometric shape.
3. The method of claim 2, further comprising the step of disposing the geometric shape within an outer cylinder.
4. The method of claim 2, comprising the further steps of:
- forming the rolled coil as a first coil and a second coil;
- attaching a first end of the first coil to a first end of the mandrel;
- connecting a first end of the second coil to a second end of the mandrel; and
- counter-coiling the first coil and the second coil about the mandrel.
5. The method of claim 1, further comprising the step of forming the geometric shape from the coated foil pattern as a stacked set of plates.
6. The method of claim 5, further comprising the step of disposing the geometric shape within an outer housing, said housing having a generally rectangular shape.
7. The method of claim 1, comprising the further steps of:
- forming the geometric shape having an inlet end and an outlet end; and progressively increasing an aperture size in the aperture pattern in a direction from the geometric shape inlet end to the outlet end.
8. The method of claim 1, further comprising the step of providing a plurality of catalyst materials for the at least one catalyst coating.
9. The method of claim 8, further comprising the step of disposing the plurality of catalyst materials in a predetermined pattern within the geometric shape.
10. The method of claim 1, further comprising the step of shaping the metal foil to form a non-repeating pattern.
4567630 | February 4, 1986 | Ishida et al. |
4847966 | July 18, 1989 | Kuchelmeister |
5394610 | March 7, 1995 | Stoephasius et al. |
5406704 | April 18, 1995 | Retallick |
5436216 | July 25, 1995 | Toyao et al. |
5437099 | August 1, 1995 | Retallick et al. |
5516383 | May 14, 1996 | Jha et al. |
5628928 | May 13, 1997 | Rolf |
5657923 | August 19, 1997 | Sheller |
5791044 | August 11, 1998 | Whittenberger et al. |
5852274 | December 22, 1998 | Watanabe et al. |
5985220 | November 16, 1999 | Hughes |
6329139 | December 11, 2001 | Nova et al. |
7141812 | November 28, 2006 | Appleby et al. |
7223373 | May 29, 2007 | Maude |
7235218 | June 26, 2007 | Bowe |
7300635 | November 27, 2007 | Bowe et al. |
20030083196 | May 1, 2003 | Korotkikh et al. |
20030235272 | December 25, 2003 | Appleby et al. |
20050042151 | February 24, 2005 | Alward et al. |
20060130327 | June 22, 2006 | Pettit et al. |
20070207186 | September 6, 2007 | Scanlon et al. |
20080073600 | March 27, 2008 | Appleby et al. |
Type: Grant
Filed: Dec 20, 2004
Date of Patent: Jun 29, 2010
Patent Publication Number: 20060130327
Assignee:
Inventors: William H Pettit (Rochester, NY), Gerald E Voecks (La Crescenta, CA)
Primary Examiner: Rick K Chang
Attorney: Harness, Dickey & Pierce, P.L.C.
Application Number: 11/019,036
International Classification: B21D 51/16 (20060101);